Semiconductor substrate, light-emitting device, and method for producing the same

ABSTRACT

A method for producing a semiconductor substrate of the present invention, includes the steps: forming a first patterned mask containing a material having a growth suppressing effect on a lower substrate; growing a semiconductor crystal on the lower substrate via the first patterned mask to form a first semiconductor crystal layer; forming a second patterned mask containing a material having a growth suppressing effect on or above the lower substrate, the second patterned mask at least having a surface which is positioned at a level different from a level of a surface of the first patterned mask, with respect to a surface of the lower substrate; and growing a semiconductor crystal on or above the lower substrate via the second patterned mask to form a second semiconductor crystal layer.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a method for growing, on a lowersubstrate, a crystal of high quality having a lattice constant differentfrom that of a lower substrate, and a semiconductor substrate obtainedby such a method. The present invention further relates to a method forgrowing a crystal to obtain a highly reliable device with highperformance by producing a light-emitting element and an electronicelement on a semiconductor substrate, and a device obtained by such amethod. In particular, the present invention relates to a method forgrowing a crystal preferably used for producing a gallium nitride (GaN)type blue light emitting element having a high efficiency and highreliability and a light-emitting element obtained by such a method.

[0003] 2. Description of the Related Art

[0004] An optoelectronic integrated circuit (OEIC) is a device which iscapable of processing a large amount of information at a high speed byintegrating an optical element and an Si-type LSI on the same substrate.The OEIC is expected as an indispensable device in an advancedinformation society and has been studied for such a reason.

[0005] In the field of an Si-type LSI, SOI, SIMOX, and the like aresuggested as an ultra-fast next generation integrated circuits with lowpower consumption, and there is an increasing demand for technicaldevelopment of SOI, SIMOX, and the like.

[0006] The main purpose in the field of an optical element is to developa technique of producing an AlGaAs laser structure on an Si substrate.However, a difference in a lattice constant and a difference in acoefficient of thermal expansion between an AlGaAs crystal and an Sicrystal of a substrate is large, thereby making it very difficult togrow an AlGaAs crystal having good crystallinity on an Si substrate. Inrealizing such a semiconductor device, characteristics of an underlyingcrystal layer for producing a device and a substrate are important.

[0007] In particular, a gallium nitride (GaN) type semiconductor isapplied to a short-wavelength light-emitting element (blue lightemitting element) and an electronic element which operates at a hightemperature and a high speed. In production of such a GaN typesemiconductor device, a substrate made of a material (e.g., sapphire andSiC) which is different from a GaN type semiconductor is used as asubstitute substrate. Basically, it is desirable to use a substrate madeof GaN for a substrate on which a GaN type semiconductor crystal isgrown. However, a GaN type semiconductor has a large decompressionpressure, so that a large-scale bulk crystal made of a GaN typesemiconductor cannot be produced; thus, such a substitute substrate isused.

[0008] In the case of using a substitute substrate as described above, adifference in a lattice constant or a difference in a coefficient ofthermal expansion between a crystal of a substrate material and a GaNtype semiconductor crystal is large, so that it is difficult toepitaxially grow a crystal having good crystallinity and having a smallcrystal defect or a crystal dislocation density on the substitutesubstrate. For example, in the case of using a sapphire substrate as asubstitute substrate for growing a GaN semiconductor crystal, it isknown that there will be a threading dislocation of about 10⁹ to 10¹⁰/cm² in the GaN semiconductor crystal layer grown on the sapphiresubstrate. Furthermore, in the case where the thickness of the GaNsemiconductor crystal layer exceeds about 10 μm, crystal cracks andlattice strains in the GaN semiconductor crystal layer become large.

[0009] In order to overcome the above-mentioned problems, for example,the following two methods for growing a crystal are suggested. As thefirst conventional example, a method for growing a crystal in ExtendedAbstracts 2p-Q-14, No. 1 (1997), p. 265 (The 58th Meeting, 1997); TheJapan Society of Applied Physics will be described. Referring to FIG.14, according to this method, an SiO₂ pattern 901, with openings 902, isformed on a sapphire substrate 900, and then, a GaN single crystal film903 is grown by a metal organic chemical vapor deposition (MOCVD)method, using the SiO₂ pattern 901 as a mask. In the first conventionalexample, the growth of the GaN single crystal starts from the opening902, not from a portion covered with the SiO₂ pattern 901 of thesapphire substrate 900. Thus, strains, which are caused by a differencein a lattice constant and/or a difference in a coefficient of thermalexpansion and which may cause threading dislocation, can be preventedfrom being generated in the vicinity of an interface between thesapphire substrate 900 and the GaN single crystal film 903. According tothis method, the SiO₂ pattern is effective for allowing a GaN crystal tobe selectively grown (i.e., an effect of suppressing the growth of acrystal defect), so that a defect density is measured (about 10⁵ toabout 10⁶/cm²) only in a GaN single crystal 904 above the SiO₂ pattern901 in the GaN single crystal film 903. According to this method, avalue of a defect density is decreased by 4 orders of magnitude,compared with a GaN single crystal in the case where a GaN signalcrystal film is directly grown on a sapphire substrate.

[0010] Furthermore, a method for growing a crystal in Extended Abstracts2p-Q-14, No. 1 (1997), p. 266 (The 58th Meeting, 1997); The JapanSociety of Applied Physics will be described. Referring to FIG. 15,according to this method, a GaN single crystal film 911 is grown on asapphire substrate 910 by an MOCVD method, an SiO₂ pattern 912 withopenings 913 is formed on the GaN single crystal film 911, and a GaNsingle crystal film 914 is grown by an HVPE (hydride vapor phaseepitaxy) method, using the SiO₂ pattern 912 as a mask. According to thismethod, a value of a defect density of the GaN single crystal film 914can be decreased for the same reason as that of the first conventionalexample. A defect density in the vicinity of the surface of the GaNsingle crystal film 914 is measured to be about 6×10⁷/cm². According tothis method, a value of a defect density is decreased by three orders ofmagnitude, compared with a GaN single crystal in the case where a GaNsingle crystal film is grown directly on a sapphire substrate withoutusing an SiO₂ pattern.

[0011] A semiconductor substrate having as its surface a GaN singlecrystal film produced by one of the above-mentioned first and secondconventional methods is used as a substrate for growing a GaN typesemiconductor device, whereby it is expected to realize an electronicdevice with higher performance.

[0012] However, a semiconductor substrate having as its surface a GaNsingle crystal film obtained by using one of the above-mentioned firstand second conventional methods is not sufficient for obtaining a highlyreliable semiconductor laser or an LED, or electronic elements such asan FET. For example, in order to enhance a life-span of a product in asemiconductor laser device, a defect density in the vicinity of alight-emitting region is required to be about 10⁵/cm² or less, and adefect density is desired to be equal to or lower than the order of10⁴/cm² of another III-V group (e.g., GaAs, etc.) semiconductorsubstrate.

[0013] A GaN single crystal layer produced by the first and secondconventional methods has a defect density of about 10⁵ to about 10⁷/cm²,and therefore, does not satisfy the above-mentioned condition. Alight-emitting element produced on a GaN single crystal layer havinglattice strains and a number of crystal defects has lower reliability.For example, a semiconductor laser device produced on such a GaN singlecrystal layer is confirmed to have a life-span of only about 900 hoursat a continuous oscillation under the condition of room temperature andan output of 3 mW.

[0014] According to the first conventional method, a high quality GaNcrystal having a reduced defect density is limited to that grown in aregion above an SiO₂ pattern. A crystal grown in the other region hasquality equal to that of a crystal according to the conventional methodwithout using an SiO₂ pattern. To use a semiconductor substrateincluding a GaN crystal layer having a locally reduced defect density asa substrate for growing a crystal is not practical for the reason of alimited degree of freedom of a device design.

[0015] According to the second conventional method, since an HVPE methodis used, a crystal layer which is relatively thick (about several 10 μm)for an epitaxial growth film can be obtained. The effect of the SiO₂pattern is relaxed in the vicinity of the surface of the GaN crystallayer by increasing the thickness of the crystal layer, so that defectswill be uniformly distributed in the entire surface. Accordingly, theproblem that crystal quality of the GaN crystal layer is locallyimproved as in the first conventional example can be solved. However, interms of the defect density, the second conventional example is inferiorto the first conventional example.

[0016] In addition, according to the first and second conventionalmethods, a GaN single crystal layer is produced by using an SiO₂ patternin the shape of a stripe. Thus, lattice strains are decreased in adirection vertical to the stripe of the SiO₂ pattern; however, latticestrains in a plane parallel to the stripe remain substantially equal tothat of a crystal according to the conventional method without using anSiO₂ pattern. When a GaN type semiconductor layer is grown on a GaNcrystal layer in which lattice strains having a particular directivityare introduced, lattice strains having anisotropy are propagated to theGaN type semiconductor layer.

[0017] Alternatively, it is also possible to grow a thicker GaN crystallayer (about 50 μm) on a sapphire substrate, and remove the sapphiresubstrate from the reverse surface of the GaN crystal layer, therebyobtaining a GaN substrate. However, crystal defects (more than on theorder of 10⁵/cm²) remain even in the GaN substrate thus obtained, andlattice strains having anisotropy cannot be relaxed.

SUMMARY OF THE INVENTION

[0018] A method for producing a semiconductor substrate of the presentinvention, includes the steps: forming a first patterned mask containinga material having a growth suppressing effect on a lower substrate;growing a semiconductor crystal on the lower substrate via the firstpatterned mask to form a first semiconductor crystal layer; forming asecond patterned mask containing a material having a growth suppressingeffect on or above the lower substrate, the second patterned mask atleast having a surface which is positioned at a level different from alevel of a surface of the first patterned mask, with respect to asurface of the lower substrate; and growing a semiconductor crystal onor above the lower substrate via the second patterned mask to form asecond semiconductor crystal layer.

[0019] In one embodiment of the present invention, the second patternedmask is positioned on the first semiconductor crystal layer.

[0020] In another embodiment of the present invention, the first andsecond patterned masks are patterned in such a manner that a combinationof the first and second patterned masks covers the entire surface of thelower substrate, and an area of the lower substrate covered with thesecond patterned mask is larger than an area of the lower substratecovered with the first patterned mask.

[0021] In another embodiment of the present invention, the secondpatterned mask includes a first portion and a second portion, the firstand second portions have different widths in a direction vertical to thesurface of the lower substrate, and the step of forming the firstsemiconductor crystal layer and the step of forming the secondsemiconductor crystal layer are conducted during the same crystal growthstep.

[0022] In another embodiment of the present invention, the first portionof the second patterned mask is at least partially positioned on thefirst patterned mask, and the second patterned mask has an L-shape.

[0023] In another embodiment of the present invention, the first portionof the second patterned mask is at least partially positioned on thelower substrate, and the second patterned mask has a T-shape.

[0024] In another embodiment of the present invention, a growthdirection of the second semiconductor crystal layer is at leastpartially different from a growth direction of the first semiconductorcrystal layer.

[0025] In another embodiment of the present invention, the firstsemiconductor crystal layer is formed in the vicinity of openings in thefirst patterned mask, whereby the first semiconductor crystal layer hasopenings on the lower substrate and the first patterned mask.

[0026] In another embodiment of the present invention, the lowersubstrate includes a sapphire substrate and a lower semiconductorcrystal layer provided on an upper side of the sapphire substrate in acrystal growth direction.

[0027] In another embodiment of the present invention, the materialhaving a growth suppressing effect is selected from the group consistingof SiO₂ and SiN_(x), and the first and second patterned masks areindependently selected from the group consisting of SiO₂ and SiN_(x).

[0028] In another embodiment of the present invention, the first andsecond semiconductor crystal layers are selected from the groupconsisting of GaN, InGaN, and AlGaN.

[0029] A semiconductor substrate of the present invention, includes: afirst patterned mask containing a material having a growth suppressingeffect, provided on a lower substrate; a first semiconductor crystallayer grown on the lower substrate via the first patterned mask; asecond patterned mask containing a material having a growth suppressingeffect, provided on or above the lower substrate, at least having asurface which is positioned at a level different from a level of asurface of the first patterned mask, with respect to a surface of thelower substrate; and a second semiconductor crystal layer grown on orabove the lower substrate via the second patterned mask.

[0030] A method for producing a semiconductor substrate of the presentinvention, includes the steps of: forming an n-th patterned maskcontaining a material having a growth suppressing effect on or above alower substrate, wherein n is an integer of 1 or more; growing a nitridesemiconductor crystal on or above the lower substrate via the n-thpatterned mask to form an n-th nitride semiconductor crystal layer;forming an (n+1)-th patterned mask containing a material having a growthsuppressing effect on or above the lower substrate, the (n+1)-thpatterned mask at least having a surface which is positioned at a leveldifferent from a level of a surface of the n-th patterned mask, withrespect to a surface of the lower substrate; and growing a nitridesemiconductor crystal on or above the lower substrate via the (n+1)-thpatterned mask to form an (n+1)-th nitride semiconductor crystal layer.

[0031] In one embodiment of the present invention, the first to (n+1)-thpatterned masks are patterned in such a manner that a combination of thefirst to (n+1)-th patterned masks covers the entire surface of the lowersubstrate.

[0032] In another embodiment of the present invention, the n-thpatterned mask and the (n+1)-th patterned mask are respectivelypatterned in a stripe shape, and a direction of the stripe of the n-thpatterned mask is twisted from a direction of the stripe of the (n+1)-thpatterned mask.

[0033] In another embodiment of the present invention, the direction ofthe stripe of the n-th patterned mask and the direction of the stripe ofthe (n+1)-th patterned mask have an angle difference of about 120°.

[0034] In another embodiment of the present invention, the direction ofthe stripe of the n-th patterned mask and the direction of the stripe ofthe (n+1)-th patterned mask have an angle difference of about 90°.

[0035] In another embodiment of the present invention, a width of thestripe of the (n+1)-th patterned mask is equal to or larger than a widthof the stripe of the n-th patterned mask.

[0036] In another embodiment of the present invention, the materialhaving a growth suppressing effect is made of SiO₂ or SiN_(x), and thefirst to (n+1)-th patterned masks are independently made of SiO₂ orSiN_(x).

[0037] In another embodiment of the present invention, the lowersubstrate includes at least a lower nitride semiconductor crystal layerprovided on an upper surface of the lower substrate, and a direction ofthe stripe of the n-th patterned mask is equal to a <1-100> direction ora <11-20> direction of a crystal of the nitride semiconductor crystallayer.

[0038] In another embodiment of the present invention, the lowersubstrate includes at least a lower nitride semiconductor crystal layerprovided on an upper side of the lower substrate in a crystal growthdirection, the semiconductor substrate includes the first, second andthird nitride semiconductor crystal layers, and a combination ofdirections of the first, second and third patterned masks consists of acombination of [1-100], [10-10], and [01-10] directions of a crystal ofthe nitride semiconductor crystal.

[0039] In another embodiment of the present invention, the n-th nitridesemiconductor crystal layer is made of Al_(x)In_(y)Ga_(z)N (wherex+y+z=1, 0≦x≦1 , 0≦y≦1, and 0≦z≦1).

[0040] In another embodiment of the present invention, the n-th nitridesemiconductor crystal layer or the (n+1)-th nitride semiconductorcrystal layer has a thickness of about 5 μm or more.

[0041] In another embodiment of the present invention, the lowersubstrate includes a substrate body and a lower nitride semiconductorcrystal layer provided on an upper side of the substrate body in acrystal growth direction, the method further including the step ofremoving at least the substrate body from a crystal structure includingthe (n+1)-th nitride semiconductor crystal layer after the step offorming the (n+1)-th nitride semiconductor crystal layer.

[0042] A semiconductor substrate of the present invention, includes: ann-th patterned mask containing a material having a growth suppressingeffect provided on or above a lower substrate, wherein n is an integerof 1 or more; an n-th nitride semiconductor crystal layer grown on orabove the lower substrate via the n-th mask; an (n+1)-th patterned maskcontaining a material having a growth suppressing material provided onor above the lower substrate, the (n+1)-th mask at least having asurface which is positioned at a level different from a level of asurface of the n-th mask, with respect to a surface of the lowersubstrate; and an (n+1)-th nitride semiconductor crystal layer grown onor above the lower substrate via the (n+1)-th patterned mask.

[0043] A light-emitting device produced by using the above-mentionedsemiconductor substrate is provided.

[0044] Thus, the invention described herein makes possible theadvantages of (1) providing a semiconductor substrate including anitride semiconductor crystal layer with a crystal defect density and athreading dislocation surface density sufficiently reduced, and a methodfor producing the same; (2) providing a semiconductor substrateincluding a nitride semiconductor crystal layer with no lattice strainshaving anisotropy introduced thereto, and a method for producing thesame; and (3) providing a highly reliable semiconductor device with highperformance, using a semiconductor substrate including a nitridesemiconductor crystal layer with improved crystallinity as a substratefor growth, and a method for producing the same.

[0045] These and other advantages of the present invention will becomeapparent to those skilled in the art upon reading and understanding thefollowing detailed description with reference to the accompanyingfigures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0046]FIG. 1 is a cross-sectional view of a semiconductor substrate inEmbodiment 1 of the present invention.

[0047]FIG. 2 is a cross-sectional view of a semiconductor substrate inEmbodiment 2 of the present invention.

[0048]FIG. 3 is a cross-sectional view of a semiconductor substrate inEmbodiment 3 of the present invention.

[0049]FIG. 4 is a cross-sectional view of a semiconductor substrate inEmbodiment 4 of the present invention.

[0050]FIG. 5 is a cross-sectional view of a semiconductor substrate inEmbodiment 5 of the present invention.

[0051]FIG. 6 is a cross-sectional view of a semiconductor laser devicein Embodiment 6 of the present invention.

[0052]FIGS. 7A and 7B are views illustrating the steps of producingsemiconductor substrates in Embodiments 7 and 8 of the presentinvention.

[0053]FIG. 8 is a view illustrating the steps of producing thesemiconductor substrates in Embodiments 7 and 8 of the presentinvention.

[0054]FIGS. 9A and 9B are views illustrating the steps of producing thesemiconductor substrates in Embodiments 7 and 8 of the presentinvention.

[0055]FIGS. 10A and 10B are views each illustrating the steps ofproducing the semiconductor substrate in Embodiment 7 of the presentinvention.

[0056]FIGS. 11A and 11B are views each illustrating a semiconductorsubstrate in Embodiment 9 of the present invention.

[0057]FIGS. 12A and 12B are views illustrating a semiconductor substratein Embodiment 10 of the present invention.

[0058]FIG. 13 is a cross-sectional view of a semiconductor laser devicein Embodiment 11 of the present invention.

[0059]FIG. 14 is a cross-sectional view of a semiconductor substratehaving a GaN crystal film on its surface in a first conventionalexample.

[0060]FIG. 15 is a cross-sectional view of a semiconductor substratehaving a GaN crystal film on its surface in a second conventionalexample.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0061] The present invention will be described by way of illustrativeembodiments with reference to the drawings.

[0062] The term “growth suppressing effect” used in the specificationand the attached claims of the present application refers to “an effectof suppressing a crystal growth on a mask”. In addition, the term“twisted” is used herein to refer to a positional relationship in whichtwo lines are disposed, without crossing in the same plane, so as to benot in parallel to each other.

[0063] Embodiment 1

[0064] A method for growing a crystal in the present embodiment will bedescribed.

[0065] First, a GaN layer 101 is grown to a thickness of about 4 μm,using trimethyl gallium (TMG) and ammonia (NH₃) as materials, on asapphire substrate 100 having a C-plane as its surface placed in apredetermined growth chamber. The sapphire substrate 100 and the GaNlayer 101 are included in a lower substrate. The GaN layer 101 is alower semiconductor crystal layer as well as a lower nitridesemiconductor crystal layer.

[0066] Then, in order to form a first patterned mask, a film (thickness:about 200 nm) made of a growth suppressing material (SiO₂) is formed onthe GaN layer 101 by sputtering. A method for forming the SiO₂ film isnot limited to sputtering. Other methods, such as vacuum vapordeposition and chemical vapor deposition (CVD), may be used.Furthermore, as a growth suppressing material, oxides such as A1 ₂O₃ andTiO₂ and SiN_(x) can be used in place of SiO₂. Then, the SiO₂ film ispatterned to a periodic stripe (width: about 7 μm; pitch: about 10 μm)by a conventional photolithography method, whereby a first SiO₂ mask 102is formed. The direction of the stripe is desirably a <1-100> directionof a crystal of the GaN layer 101.

[0067] By using the lower substrate thus obtained, a GaN crystal film103 is grown by a metal-organic-vapor-phase epitaxy (MOVPE) method. Morespecifically, the GaN crystal film 103 is grown to a thickness of about3 μm at a growth temperature of about 1050° C., using TMG and NH₃ asmaterials, in a predetermined growth chamber. The GaN crystal film 103starts growing from openings in the first mask, and is flatly grown oversubstantially the entire surface of the lower substrate due toanisotropy (i.e., a growth speed in a direction horizontal to the lowersubstrate is higher than that in a direction vertical to the lowersubstrate).

[0068] A defect density on the first mask is about 10⁵/cm² or less;however, a defect density on the sapphire substrate in the openingportions of the first mask is about 10⁷/cm². In the conventionalexample, although a laser device is formed avoiding such portions,reliability and yield are not sufficient.

[0069] Then, a second mask is formed on the GaN crystal film 103. Morespecifically, an SiO₂ film (thickness: about 200 nm) is formed bysputtering in the same way as in the first mask, and a second SiO₂ mask104 with a periodic stripe pattern (width: about 8 μm; pitch: about 10μm) is formed by a photolithography method. At this time, it isimportant that the position of the second mask is matched with theopenings in the first mask.

[0070] Then, a GaN single crystal film 105 is grown on the second SiO₂film by a MOVPE method. More specifically, GaN is grown to a thicknessof about 3 μm at a growth temperature of about 1050° C., using TMG andNH₃ as materials, in a predetermined growth chamber. Thus, asemiconductor substrate is completed.

[0071] In the GaN single crystal film 105 grown in the presentembodiment, a defect density is decreased to about 1500/cm² or less, andcrystallinity is remarkably improved.

[0072] In the case where the first mask and the second mask have astripe width of about 4 μm and a pitch of about 10 μm, and the first andsecond masks are positioned so as to be shifted by a half pitch (in thecase where the stripe width of the second mask is smaller than eachopening of the first mask) in the present embodiment, a defect densitybecomes about 5000/cm². Thus, an effect of a sufficient decrease incrystal defects is observed when compared with the case of using onlythe first mask in the conventional example. A defect density becomesrelatively small in the case where the stripe width of the second maskis larger than each opening of the first mask, and the first and secondmasks completely cover crystal threading dislocation extending upwardfrom the sapphire substrate 100. Accordingly, it is confirmed that it isimportant to form the second mask so as to completely cover the openingsof the first mask.

[0073] On the other hand, the following is found according to X-raydiffraction measurement: in the case where the stripe width of thesecond mask is smaller than each opening of the first mask, a defectdensity is decreased to some degree (about 5000/cm²), and a c-axisalignment of a GaN continuous film is improved. The following isconfirmed in the case where the stripe width of the second mask islarger than each opening of the first mask, a ω value (full width athalf maximum) of X-ray diffraction representing alignment variation isabout 4 to 6 arcminutes; however, in the case where the stripe width ofthe second mask is smaller than each opening of the first mask,alignment variation (ω value) of a crystal is reduced to 2 arcminutes ina wafer plane. Thus, in the case where an LED, a semiconductor laserdevice, or the like is produced under the condition that the stripewidth of the second mask is smaller than each opening of the first mask,a light-emitting efficiency is degraded compared with the case where thestripe width of the second mask is larger than each opening of the firstmask; however, a light-emitting efficiency in a wafer plane anduniformity of a threshold current of a laser are improved, whichenhances the production yield of a device. Accordingly, it is importantto select the relationship between the size of each opening of the firstmask and the stripe width of the second mask, depending upon requiredcharacteristics of a light-emitting device. Furthermore, if the firstand second masks are formed of the same material, the same vapordeposition apparatus can be used, and quality of crystal films can bestabilized by the same growth suppressing effect (in the case of givinga high priority to a light-emitting efficiency, the stripe width of thesecond mask should be prescribed to be larger than each opening of thefirst mask; in the case of giving a high priority to uniformity ofcharacteristics and yield, the stripe width of the second mask should beprescribed to be smaller than each opening of the first mask).

[0074] Embodiment 2

[0075]FIG. 2 shows the second embodiment. The second embodiment isdifferent from the first embodiment in that a GaN crystal film 203 grownby using a first mask is not a continuous film, and a second mask isformed on the GaN crystal film 203 grown in the shape of an island.

[0076] First, a GaN layer 201 is grown to a thickness of about 4 μm on asapphire substrate 200 in the same way as in Embodiment 1. In the caseof the second embodiment, a first GaN crystal film 203 grown by using afirst SiO₂ mask 202 is prescribed to have a thickness of about 1 μm, awidth of about 7 μm, and a pitch of about 10 μm. Then, a second GaNsingle crystal film 205 (thickness: about 4 μm) is grown by using asecond SiO₂ mask 204 (thickness: about 200 nm). A defect density isabout 800/cm² or less. Thus, a satisfactory crystal is obtained. This isan effect that the GaN single crystal film 205 grows only from sidesurfaces 206 where there are few defects in the first GaN crystal.

[0077] Embodiment 3

[0078] The third embodiment will be described with reference to FIG. 3.In Embodiment 1, it is required to conduct crystal growth of GaN for apatterned mask by two steps; however, in Embodiment 3, one step ofcrystal growth suffices, which results in a cost advantage.

[0079] First, an SiO₂ film is formed to a thickness of about 200 nm on asapphire substrate 300 with a GaN layer 301 formed thereon, bysputtering in the same way as in Embodiment 1. The SiO₂ film is etchedto a stripe shape (width: about 4 μm; pitch: about 8 μm) by aconventional photolithography method, whereby a first SiO₂ mask 302 isformed. Then, an SiO₂ film is formed on the resultant substrate in thesame way as the above, whereby a second lower SiO₂ mask 303 in the shapeof a stripe (width: about 2 μm; pitch: about 8 μm) is formed on thefirst SiO₂ mask 302. Then, a portion other than the lower SiO₂ mask 303is covered with a photoresist film by conventional photolithography.More specifically, a photoresist such as AZ (produced by SHIPLEY isspin-coated over the entire surface of the GaN layer 301, the firstSiO₂mask 302, and the lower SiO₂ mask 303. Then, only the lower SiO₂mask 303 is exposed to light and developed, and the photoresist film isremoved. Furthermore, an SiO₂ film is formed to obtain a second upperSiO₂ mask 304 in the shape of a stripe (width: about 5 μm; pitch: about8 μm). Thereafter, the above-mentioned photoresist film is removed witha solvent such as acetone. The second lower SiO₂ mask 303 and the secondupper SiO₂ mask 304 form a second mask in the shape of a letter “L”. GaNis grown by a MOVPE method by using the resultant substrate. Morespecifically, a GaN single crystal film 305 is grown to a thickness ofabout 3 μm at a growth temperature of about 1050° C., using TMG and NH₃as materials, in a predetermined growth chamber. Thus, a semiconductorsubstrate is completed.

[0080] Herein, crystal growth of the GaN single crystal film 305 startsfrom openings of the first SiO₂ mask 302. Then, the crystal growth in adirection vertical to the substrate stops at the second upper SiO₂ mask304. Thereafter, the crystal growth proceeds in a direction parallel tothe substrate. The crystal growth also starts from openings of thesecond upper SiO₂ mask 304 in a direction vertical to the substrate.Finally, a crystal is grown uniformly over the entire surface of thesubstrate.

[0081] In the present embodiment, dislocation in a direction vertical tothe substrate, which is generated from the interface between the GaNlayer 301 and the sapphire substrate 300, stops at the second upper SiO₂mask 304, and dislocation in a direction horizontal to the substratestops at the second lower SiO₂ mask 303. Thus, the obtained GaN singlecrystal film 305 is of satisfactory quality (i.e., a defect density isabout 600/cm² or less).

[0082] Embodiment 4

[0083] The fourth embodiment will be described with reference to FIG. 4.

[0084] First, an SiO₂ film is formed to a thickness of about 200 nm on asapphire substrate 400 with a GaN layer 401 formed thereon, bysputtering in the same way as in Embodiment 1. The SiO₂ film is etchedto a stripe shape (width: about 4 μm; pitch: about 8 μm) by aconventional photolithography method, whereby a first SiO₂ mask 402 isformed. Then, a second lower SiO₂ mask 403 is formed to a stripe shape(width: about 2 μm; pitch: about 8 μm) on the GaN layer 401. Then, aportion other than the lower SiO₂ mask 403 is covered with a photoresistfilm by conventional photolithography. More specifically, a photoresistsuch as AZ (produced by SHIPLEY) is spin-coated over the entire surfaceof the GaN layer 401 and the first SiO₂ mask 402. Then, only the lowerSiO₂ mask 403 is exposed to light and developed, and the photoresistfilm is removed. Furthermore, a second upper SiO₂ mask 404 in the shapeof a stripe (width: about 5 μm; pitch: about 8 μm) is formed on-thesecond lower SiO₂ mask 403. Thereafter, the above-mentioned photoresistfilm is removed with a solvent such as acetone. The second lower SiO2mask 403 and the second upper SiO₂ mask 404 form a second mask in theshape of a letter “T”. GaN is grown by a MOVPE method by using theresultant substrate. More specifically, a GaN single crystal film 405 isgrown to a thickness of about 3 μm at a growth temperature of about1050° C., using TMG and NH₃as materials, in a predetermined growthchamber. Thus, a semiconductor substrate is completed.

[0085] Herein, crystal growth of the GaN single crystal film 405 startsfrom openings of the first SiO₂ mask 402. Then, the crystal growth in adirection vertical to the substrate stops at the second upper SiO2 mask404. Thereafter, the crystal growth proceeds in a direction parallel tothe substrate. The crystal growth also starts from openings of thesecond upper SiO₂ mask 404 in a direction vertical to the substrate.Finally, a crystal is grown uniformly over the entire surface of thesubstrate.

[0086] In the present embodiment, dislocation in a direction vertical tothe substrate, which is generated from the interface between the GaNlayer 401 and the sapphire substrate 400, stops at the second upper SiO₂mask 404, and dislocation in a direction horizontal to the substratestops at the second lower SiO₂ mask 403. Thus, the obtained GaN singlecrystal film 405 is of satisfactory quality (i.e., a defect density isabout 800/cm² or less).

[0087] Embodiment 5

[0088] The fifth embodiment will be described with reference to FIG. 5.

[0089] First, in order to form a first patterned mask, a film made of agrowth suppressing material (SiO₂) is formed to a thickness of about 200nm by sputtering on a sapphire substrate 500 having a C-plane as itssurface on which a GaN layer 501 is formed. A method for forming theSiO₂film is not limited to sputtering. Another method, such as vacuumvapor deposition or CVD, may be used. Furthermore, as a growthsuppressing material, oxides such as Al₂O₃ and TiO₂ and SiN_(x) can beused in place of SiO₂. Then, openings in the shape of a stripe (width:about 3 μm; pitch: about 100 μm) are provided in the SiO₂ film by aconventional photolithography method, whereby a first SiO₂ mask 502 isformed. The direction of the stripes is desirably <1-100> with respectto the GaN layer 501.

[0090] GaN is grown by a MOVPE method by using the resultant substrate.More specifically, GaN 503 is grown to a thickness of about 0.5 μm at agrowth temperature of about 1050° C., using TMG and NH₃ as materials, ina predetermined growth chamber. The GaN 503 is grown only at edgeportions of the first SiO₂ mask 502 without burying the first SiO₂ mask502. The edge portions have a low potential with respect to otherportions, so that the GaN 503 is of satisfactory quality without anydefects.

[0091] Then, a second mask is formed on the resultant substrate. Morespecifically, SiO₂ is deposited to a thickness of about 200 nm bysputtering in the same way as in the first SiO₂ mask 502, whereby asecond SiO₂ mask 504 is formed in the shape of a stripe (width: 5 μm;pitch: 100 μm) by a photolithography method. It is important that thepositions of light-blocking portions are substantially matched with theopenings of the first SiO₂ mask 502.

[0092] Then, a GaN single crystal film 505 is grown by a MOVPE method,by using the resultant substrate. More specifically, GaN is grown to athickness of about 3 μm at a growth temperature of about 1050° C., usingTMG and NH₃ as materials, in a predetermined growth chamber. Thus, asemiconductor substrate is completed.

[0093] In the GaN single crystal film 505 grown in the presentembodiment, a defect density is decreased to about 1000/cm² or less overthe entire surface thereof, and crystallinity is remarkably improved.

[0094] Herein, it is important that the light-blocking portions of thesecond SiO₂ mask 504 cover the openings of the first SiO₂ mask 502.

[0095] Embodiment 6

[0096] The sixth embodiment will be described with reference to FIG. 6.Herein, the same reference numerals as those in Embodiment 1 denote thesame elements as those herein.

[0097] A semiconductor laser device in the present embodiment includesan n-GaN contact layer 106, an n-Al_(0.1)Ga_(0.9)N cladding layer 107,an n-GaN guide layer 108, a multi quantum-well structure active layer109 including 5 In_(0.2)Ga_(0.8)N quantum-well layers and 6In_(0.05)Ga_(0.95)N barrier layers, an Al_(0.2)Ga_(0.8)N evaporationpreventing layer 110, a p-GaN guide layer 111, a p-Al_(0.1)Ga_(0.9)Ncladding layer 112, a p-GaN contact layer 113, a p-type electrode 114,an n-type electrode 115, and an SiO₂ insulating film 116.

[0098] According to the present invention, the surface of the sapphiresubstrate 100 may have another orientation, such as an a-plane, anr-plane, and an m-plane. Furthermore, a GaN substrate, an SiC substrate,a spinnel substrate, an MgO substrate, an Si substrate, and a GaAssubstrate can be used in place of a sapphire substrate. Particularly inthe case of using a GaN substrate, compared with the case of using asapphire substrate, at least the following advantages are obtained: adifference in a lattice constant between the substrate and a galliumnitride type semiconductor material deposited on the substrate issmaller, and a film with satisfactory crystallinity can be obtained.Furthermore, the GaN substrate is more likely to be cleaved, so that itis easier to produce a laser resonator by cleavage. The cladding layer107 and the cladding layer 112 may be made of a mixed crystal containingthree elements (AlGaN) having an Al mole fraction other thanAl_(0.1)Ga_(0.9)N. In this case, when an Al mole fraction is increased,a difference in an energy gap and a difference in a refractive indexbetween the active layer and the cladding layer becomes larger, so thatcarriers and light are confined in the active layer, which furtherdecreases an oscillation threshold current and improves temperaturecharacteristics. Furthermore, when an Al mole fraction is decreased tosuch a degree that carriers and light can be confined, the mobility ofcarriers in the cladding layer becomes large. Therefore, the resistanceof a semiconductor laser device can be decreased. Furthermore, thecladding layers 107 and 112 may be made of a mixed crystal semiconductorcontaining a trace amount of another element in addition to theabove-mentioned three elements, and the mole fractions of a mixedcrystal are not required to be the same between the cladding layer 107and the cladding layer 112.

[0099] The guide layers 108 and 111 may be made of any material whichallows an energy gap therebetween to have a value between an energy gapof the quantum-well layers included in the active layer 109 and a energygap of the cladding layers 107 and 112. For example, a mixed crystalcontaining three elements (e.g., InGaN or AlGaN) may be used.Furthermore, it is not necessary to dope a donor or an acceptor over theentire guide layers 108 and 111, and only a portion thereof on the sideof the active layer 109 may be non-doped. Furthermore, the entire guidelayers 108 and 111 may be non-doped. In this case, there is an advantagethat the number of carriers present in the guide layers 108 and 111becomes small, light absorption by free carriers is decreased, and anoscillation threshold current can be further reduced.

[0100] With the quantum-well layers and the barrier layers included inthe active layer 109, mole fractions should be set in accordance with arequired laser oscillation wavelength. In the case where it is desirableto make an oscillation wavelength longer, the In mole fraction of thequantum-well layers is increased. In the case where it is desired toshorten an oscillation wavelength, the In mole fraction of thequantum-well layers is decreased. Furthermore, the quantum-well layersand the barrier layers maybe made of a mixed crystal semiconductorcontaining four or more elements including a trace amount of anotherelement in addition to a mixed crystal containing three elements(InGaN). The barrier layers may be made of GaN.

[0101] In the present embodiment, the evaporation preventing layer 110is formed in contact with the active layer 109. The purpose of this isto prevent the active layer 109 from evaporating during an increase in agrowth temperature. Therefore, any material can be used for theevaporation preventing layer 110 as long as it protects the active layer109. For example, a mixed crystal containing three elements (AlGaN)having another Al mole fraction and GaN may be used. Furthermore, Mg maybe doped into the evaporation preventing layer 110. In this case, thereis an advantage that holes can be easily injected from the guide layer111 and the cladding layer 112. Furthermore, in the case where the Inmole fraction of the quantum-well layers included in the active layer109 is small, the quantum-well layers are not evaporated, so that theevaporation preventing layer 110 is not required to be formed. Even ifthe evaporation preventing layer 110 is not formed, characteristics of agallium nitride type semiconductor laser device in the presentembodiment will not be impaired.

[0102] Hereinafter, a method for producing the above-mentioned galliumnitride type semiconductor laser device will be described with referenceto FIG. 6.

[0103] In the following description, the case of using a MOVPE method isshown. However, any method which is capable of epitaxially growing GaNmay be used. For example, another vapor growth method such as molecularbeam epitaxy (MBE) or HVPE can be used.

[0104] First, the contact layer 106 doped with Si is grown to athickness of about 3 μm at a growth temperature of about 1050° C., usingTMG, NH₃, and a silane gas (SiH₄) as materials, on the substrateproduced in Embodiment 1 placed in a predetermined growth chamber. Then,trimethyl aluminum (TMA) is added to the materials, and the claddinglayer 107 doped with Si is grown to a thickness of about 0.4 μm at agrowth temperature of about 1050° C. TMA is removed from the materials,and the guide layer 108 doped with Si is grown to a thickness of about0.1 μm at a growth temperature of about 1050° C.

[0105] Next, the growth temperature is lowered to about 750° C., and 5barrier layers (thickness: about 5 nm) and 5 quantum-well layers(thickness: about 2 nm) are alternately grown and the barrier layer(thickness: about 5 nm) is grown, using TMG, NH₃ and trimethyl indium(TMI), whereby the active layer 109 (total thickness: about 40 nm) isproduced. Then, the evaporation preventing layer 110 is grown to athickness of about 20 nm at a growth temperature of about 750° C., usingTMG, TMA, and NH₃ as materials.

[0106] Next, the growth temperature is raised to about 1050° C., and theguide layer 111 doped with Mg is grown to a thickness of about 0.1 μm,using TMG, NH₃, and bisethylcyclopentadienyl magnesium (EtCP₂Mg) asmaterials. TMA is added to the materials, and the cladding layer 112 isgrown to a thickness of about 0.4 μm at a growth temperature of about1050° C. TMA is removed from the materials, and the contact layer 113doped with Mg is grown to a thickness of about 0.2 μm at a growthtemperature of about 1050° C. Thus, a gallium nitride type epitaxialwafer is completed. Thereafter, the wafer is annealed in a nitrogen gasatmosphere at about 800° C. , whereby the Mg-doped p-type layers arerendered low-resistant.

[0107] Furthermore, etching is conducted from the top surface of thecontact layer 113 so as to obtain a stripe shape (width: about 200 μm)by using conventional photolithography and dry etching until the contactlayer 106 is exposed, whereby a mesa structure is produced. Next, usingthe photolithography and dry etching similar to the above, the remainingcontact layer 113 and the cladding layer 112 are etched. At this time, astripe-shaped ridge structure should be positioned about 3 μm or moreaway from both ends of the mesa structure with a width of about 200 μm.In the present embodiment, the ridge structure is formed about 10 μmaway from the end of the mesa structure on the side where the n-typeelectrode 115 is to be formed. If the ridge structure is positioned soas to be close to the n-type electrode 115 as described above, theelectric resistance of the device is decreased, and the working voltageis reduced. Furthermore, the dry etching is stopped so as not to etchthe active layer 109. Thus, the active layer 109 is protected frometching damage, which prevents a decrease in reliability and an increasein an oscillation threshold current.

[0108] The insulating film 116 is formed to a thickness of about 200 nmas a current blocking-layer on the side surfaces of the ridge structureand on the surface of the p-type layer excluding the ridge. The p-typeelectrode 114 made of nickel and gold is formed on the surface of theinsulating layer 116 and the contact layer 113, and the n-type electrode115 made of titanium and aluminum is formed on the surface of thecontact layer 106 exposed by etching. Thus, a gallium nitride type laserdevice wafer is completed.

[0109] Thereafter, the wafer thus obtained is cleaved in a directionvertical to the ridge stripe to form a resonance plane, and the wafer isdivided into chips. Each chip is mounted on a stem, and each electrodeis connected to each lead terminal by wire bonding. Thus, a galliumnitride type semiconductor laser device is completed.

[0110] In the semiconductor laser device produced as described above,satisfactory laser characteristics (oscillation wavelength: about 410nm; oscillation threshold value: about 20 mA) are obtained. Furthermore,due to a decrease in crystal defects, the semiconductor laser devicethus obtained is highly reliable (about 10⁵ hours at about 60° C.).Furthermore, a ratio of laser devices having crystal defects isremarkably decreased, with a yield being about 80% or higher.

[0111] In the present embodiment, thicknesses of each quantum-well layerand each barrier layer included in the active layer 109 are about 2 nmand about 5 nm, respectively. However, as long as the thickness of eachquantum-well layer and each barrier layer is prescribed to be about 10nm or less, the same effects can be obtained irrespective ofembodiments. Furthermore, the number of quantum-well layers in theactive layer 109 may be 2, 3 or 4. Alternatively, a single quantum-wellstructure active layer may be used.

[0112] In the present embodiment, sapphire, which is an insulator, isused for the substrate, so that the n-type electrode 115 is formed onthe surface of the contact layer 106 exposed by etching. However, ifGaN, SiC, Si, GaAs, or the like having an n-type insulating property isused, the n-type electrode 115 may be-formed on the reverse surface ofthe substrate. In this case, the mesa structure with a width of about200 μm should be positioned at least about 3 μm away from both ends ofthe semiconductor laser device chip. P-type structures and n-typestructures may be reversed.

[0113] Embodiment 7

[0114] Referring to FIG. 7A, a method for growing a crystal inEmbodiment 7 will be described. FIG. 7A is a cross-sectional view of anitride semiconductor to be formed.

[0115] First, a GaN layer 601 is grown to a thickness of about 2 μm,using TMG and NH₃ as materials, on a sapphire substrate 600 having aC-plane as its surface placed in a predetermined growth chamber. Thesapphire substrate 600 and the GaN layer 601 are included in a lowersubstrate. The GaN layer 601 is a lower semiconductor crystal layer aswell as a lower nitride semiconductor crystal layer.

[0116] Then, in order to form a first mask pattern, a film (thickness:about 100 nm) made of a growth suppressing material (SiO₂) is formed onthe GaN layer 601 by sputtering. A method for forming the SiO₂ film isnot limited to sputtering. Another method, such as CVD, electron beam(EB) vapor deposition, or vacuum vapor deposition, may be used.Furthermore, as a growth suppressing material, oxides such as Al₂O₃ andTiO₂ and SiN_(x) can be used in place of SiO₂. Then, the SiO₂ film ispatterned to a periodic stripe (width w: about 7 μm; pitch d: about 10μm) by a conventional photolithography method, whereby a first maskpattern 602 is formed. FIG. 7B is a plan view of a nitride semiconductorto be formed. As shown in FIG. 7B, the direction of the stripe isprescribed to be a [1-100] direction of a GaN crystal.

[0117] By using the substrate with the first mask pattern thus obtained,a first GaN film 604 is grown by a MOVPE method. More specifically, thefirst GaN film 604 is grown to a thickness of about 5 μm at a growthtemperature of about 1050° C., using TMG and NH₃ as materials, in apredetermined growth chamber. Thus, the first step is completed. Thefirst GaN film 604 starts growing from openings 605 in the first maskpattern 602, and is flatly grown over substantially the entire surfaceof the sapphire substrate due to anisotropy (i.e.; a growth speed in adirection horizontal to the substrate, particularly, in a <11-20>direction with respect to a GaN crystal, is higher than that in adirection vertical to the substrate).

[0118] Portions of the first GaN film 604 on the first mask pattern 602grown in a direction vertical to the stripe of the first mask pattern602 have a very weak inter-atom bond with respect to the first maskpattern 602 (i.e., these portions are not epitaxially grown from thefirst mask pattern 602); therefore, lattice strains are not caused inthese portions. However, lattice strains remain in a direction parallelto the stripe due to a difference in a lattice constant between the GaNlayer 601 and the sapphire substrate 600, and the lattice strains arealso reflected onto the first GaN film 604. During the first step,problems of lattice strains and a high threading dislocation density arenot overcome. Thus, when a semiconductor laser is formed on the firstGaN film 604 including the lattice strains and having a high threadingdislocation density, a continuous oscillation time of the device at roomtemperature is about 900 hours. This oscillation life does not satisfyreliability of the device.

[0119] Furthermore, as described above, since the portions of the firstGaN film 604 immediately above the first mask pattern 602 have a veryweak inter-atom bond with respect to the first mask pattern 602, theseportions are unlikely to be influenced by thermal strains from theunderlying layer (i.e., the sapphire substrate 600). However, a GaNcrystal above the openings in the first mask pattern 602 is morestrongly influenced by thermal strains from the underlying layer (i.e.,the sapphire substrate 600).

[0120] The portions of the first GaN film 604 immediately above thefirst mask pattern 602 has a threading dislocation density of the orderof 10⁴ to 10⁵/cm². The portions of the first GaN film 604 immediatelyabove the openings of the first mask pattern 602 have a threadingdislocation density of the order of 10⁷ to 10 ⁸/cm². In the conventionalexample, a laser device is formed avoiding the portions includinglattice strains, thermal strains, and the like, which makes reliabilityand yield of the device insufficient.

[0121] Then, a second mask pattern 606 (FIG. 8) made of SiO₂ is formedon the surface of the first GaN film 604. More specifically, an SiO₂film (thickness: about 100 nm) formed by the same method as that of thefirst mask pattern 602 is subjected to conventional photolithography andetching, whereby the periodic second mask pattern 606 (width: about 8μm; pitch: about 10 μm) made of SiO₂ is formed. Furthermore, under thecondition that the stripe direction of the second mask pattern 606 isobserved from above the wafer, the stripe direction of the second maskpattern 606 is prescribed to be a [01-10] direction of a GaN crystal sothat it forms an angle of about 120° with respect to the stripedirection of the first mask pattern 602. FIG. 8 is a plan view of thesemiconductor device in this state. For description, FIG. 8 shows themask patterns as seen from the top.

[0122] The second mask pattern 606 is formed to have a width larger thanthat of the first mask pattern 602 by about 1 μm, so that the secondmask pattern 606 covers the surface of the underlying first GaN film 604more widely than the first mask pattern 602.

[0123] Next, a second GaN film 607 (FIG. 9A) is grown over the entiresurface of the first GaN film 604 with the second mask pattern 606formed thereon by an MOCVD method. Thus, the second step is completed.The growth of the second GaN film 607 is conducted at a substratetemperature of about 1050° C., using TMG and NH₃ as materials. Thesecond GaN film 607 has a thickness of about 5 μm. Accordingly, thesecond GaN film 607 is grown uniformly over the entire surface of thewafer including upper portions of the second mask pattern 606, and thesurface of the second GaN film 607 becomes substantially flat. FIG. 9Ais across-sectional view taken along a line a-a′ parallel to the secondmask pattern 606 in FIG. 8, and FIG. 9B is across-sectional view takenalong a line b-b′ parallel to the first mask pattern 602 in FIG. 8. Thecross-section taken along the line b-b′ is obtained from an openingportion of the first mask pattern 602, and hence, the first mask pattern602 cannot be observed in FIG. 9B.

[0124] Lattice strains in the second GaN film 607 grown during thesecond step are reduced in a direction vertical to the stripe of thesecond mask pattern 606 in the same way as in the first step, comparedwith the case where there is no second mask pattern 606. Lattice strainsin a direction parallel to the stripe of the second mask pattern 606become similar to that of the first GaN film 604. Lattice strains in thefirst GaN film 604 are reduced in a direction vertical to the first maskpattern 602 during the first step. Therefore, in the second GaN film607, lattice strains are reduced in two directions, i.e., in a directionvertical to the stripe of the first mask pattern 602 and in a directionvertical to the stripe of the second mask pattern 606.

[0125] Furthermore, a threading dislocation density of the second GaNfilm 607 produced during the second step is decreased to the order of10³/cm²in portions 608 immediately above the first and second maskpatterns 602 and 606, and crystallinity is remarkably improved.Furthermore, a threading dislocation density of portions 609 of thesecond GaN film 607 grown from the opening portions of the first maskpattern 602 is on the order of 10⁵/cm² due to lateral growth caused bythe second mask pattern 606. Furthermore, a threading dislocationdensity of portions 610 immediately above the first mask pattern 602 ison the order of about 10⁴/cm².

[0126] Furthermore, as the third step, a GaN crystal is grown on thesecond GaN film 607 by using a periodic stripe-shaped mask similar tothose used during the first and second steps. First, an SiO₂ film(thickness: about 100 nm) is formed on the second GaN film 607 by thesame method as that of the first step. The SiO₂ film is formed into aperiodic stripe by conventional photolithography and etching, whereby athird mask pattern 611 with a width of about 8 μm and a period of about10 μm is obtained. The third mask pattern 611 is disposed in such amanner that the stripe direction thereof forms an angle of about 120°with respect to any direction of the first and second mask patterns 602and 606. That is, the stripe direction of the third mask pattern 611 isa [10-10] direction. FIG. 10A is a plan view of the semiconductor devicein this state. For description, FIG. 10A shows the mask patterns as seenfrom the top.

[0127] Next, a third GaN film 612 (thickness: about 5 μm) is grown onthe second GaN film 607 with the third mask pattern 611 formed thereonin the same way as in the first and second steps. Thus, the third stepis completed. The third GaN film 612 is also grown over the entiresurface of the third mask pattern 611 made of SiO₂, and exhibits asingle film having a substantially flat surface. Furthermore, in thethird GaN film 612 formed during the third step, lattice strains in adirection vertical to the stripe of the third mask pattern 611 arefurther reduced, compared with the second GaN film 607. FIG. 10B is aview showing the semiconductor device, taken along a line a-a′ in FIG.10A.

[0128] As described above, the third GaN film 612 on the uppermostsurface produced through three steps is obtained by growing a GaNcrystal above three kinds of mask patterns 602, 606, and 611 which forman angle of about 120° with respect to each other. During the respectivesteps, lattice strains in a direction vertical to the stripes of therespective mask patterns are relaxed. Thus, the third GaN film 612 hasstrains reduced isotropically by three kinds of mask patterns which formthe same angle with each other. As a result, a semiconductor substrateincluding the third GaN film 612 having substantially no strains in anyin-plane direction is realized.

[0129] Furthermore, in the present embodiment, the stripe directions ofthe first mask pattern 602, the second mask pattern 606, and the thirdmask pattern 611 are prescribed to be [1-100], [01-10], and [10-10]. Thepresent invention is not limited thereto. If the stripe directions ofthe first, second, and third mask patterns are a <1-100> direction, andthe respective stripe directions have an angle difference of about 120°,there is an effect that substantially no strains are present in anyin-plane direction. By prescribing the stripe direction of one of thefirst to third masks to be <1-100> and prescribing the stripe directionsof the other mask patterns so that they have an angle difference ofabout 120°, an equivalent strain relaxing function is exhibited in anitride semiconductor, and lateral growth of a crystal is promoted,whereby the mask patterns can be efficiently buried. Therefore, adecrease in a threading dislocation density and strain relaxation can bemaximized.

[0130] A threading dislocation density on the surface of the third GaNfilm 612 is checked, revealing that a threading dislocation extendingstraight upward from the sapphire substrate 600 is covered with any ofthe first to third mask patterns, whereby a threading dislocation isprevented from extending through the masks. Therefore, a threadingdislocation density on the surface of the third GaN film 612 can bereduced by one or more orders of magnitude (i.e., about 10³/cm² to about10⁴/cm²), compared with the conventional technique. Although portions613 in the third GaN film 612 grown from the opening portions of thefirst mask pattern 602 are not covered with three kinds of maskpatterns, their ratio with respect to the entire area is less than about10%, and a threading dislocation is not increased in these portions.This may be because a threading dislocation is dispersed to the rightand left during the step of forming a GaN film to a total of about 15 μmor more, and a threading dislocation is substantially uniformlydistributed on the surface of the third GaN film 612 formed during thethird step.

[0131] The first, second, and third mask patterns have the samethickness and are made of the same growth suppressing material (SiO₂) inEmbodiment 7. However, these mask patterns may have differentthicknesses and be made of different growth suppressing materials. Inparticular, if the same grown suppressing material is used for thesemask patterns, the same growth chamber can be used, which isadvantageous in terms of productivity, and the same growth suppressingeffect is obtained, resulting in good controllability of growth. As amethod for growing a nitride semiconductor, an HVPE method or an MBEmethod may be used in place of the above-mentioned MOVPE method.

[0132] Furthermore, in the present embodiment, the first to thirdnitride semiconductor crystal layers are formed by using the first tothird masks. However, the present invention is not limited thereto. Forexample, it may be possible that the n-th nitride semiconductor crystallayer is formed on the n-th mask, and the (n+1)-th mask and the (n+1)-thnitride semiconductor crystal layer are formed in the same way as in then-th step. Herein, n is an integer of 1 or more. Accordingly, bysuccessively conducting a series of steps, crystal strains in a nitridesemiconductor film during each step (strains caused by a difference in alattice constant or a difference in a coefficient of thermal expansionbetween the substrate and the nitride semiconductor crystal) arereduced. Furthermore, a dislocation generated from the interface of thesubstrate will not emerge on the surface of a grown crystal film.

[0133] Even in the above case, in the same way as in the presentembodiment, it is preferable that the first to (n+1)-th masks arecombined with each other and patterned so as to cover the entire surfaceof the lower substrate. Because of this, a dislocation generated fromthe opening portions of the first mask pattern formed on the substrateor the nitride semiconductor film grown on the substrate is blocked withany of (n+1) mask patterns. Thus, a density of a threading dislocationwhich reaches the surface of the n-th nitride semiconductor film isremarkably reduced.

[0134] Furthermore, it is preferable that the n-th mask and the (n+1)-thmask are patterned to be striped, and the stripe directions of the n-thmask and the (n+1)-th mask are disposed so as to be twisted from eachother. Because of this, a nitride semiconductor film crystal coveringportions immediately above a mask pattern is unlikely to grow, due toselective growth, directly on the mask pattern, and the nitridesemiconductor film crystal covering portions immediately above a maskpattern is laterally grown from the opening portions of the mask patternin a direction vertical to the stripe direction of the mask pattern.Thus, portions of the (n+1)-th nitride semiconductor film on the(n+1)-th mask pattern grown in a direction vertical to the stripe of the(n+1)-th mask pattern have a very weak inter-atom bond with respect tothe (n+1)-th mask pattern, so that lattice strains are not caused inthese portions. However, in a direction parallel to a stripe, latticestrains are transferred from the underlying layer formed during or priorto the n-th step to the (n+1)-th nitride semiconductor film. This isalso applicable to thermal strains.

[0135] Due to the twisted positional relationship among the maskpatterns as described above, an effect of strains from the underlyinglayer can be canceled in various directions, as well as in onedirection. The above-mentioned relaxation of strains has an effect ofsuppressing an edge dislocation from being generated.

[0136] Furthermore, it is preferable that the stripe directions of then-th mask and the (n+1)-th mask are twisted from each other so as tohave an angle difference of about 120°. A nitride semiconductor mainlyhas a wurtzite structure, so that there are three kinds of equivalentdirections. These three directions have an angle difference of 120° fromeach other. By disposing the mask patterns produced during theabove-mentioned steps so that they have an angle difference of about120° from each other, these mask patterns have selection characteristicsequivalent to each other, and strains can be relaxed by an equivalentstrain relaxing function.

[0137] It is preferable that the stripe width of the (n+1)-th mask isequal to or larger than that of the n-th mask. If the stripe width of amask pattern is increased with the increase in the number of theabove-mentioned steps (i.e., an increase in n), a nitride semiconductorfilm produced during each step will have a decreased density of athreading dislocation generated from the substrate to the crystallayering direction.

[0138] A growth suppressing material may be SiO₂ or SiN_(x), and thefirst to (n+1)-th masks may be independently made of SiO₂ or SiN_(x). Amask pattern made of SiO₂ or SiN_(x) has a sufficient growth suppressingeffect.

[0139] The stripe direction of the n-th mask preferably agrees with a<1-100> direction or a <11-20> direction of a crystal of the nitridesemiconductor crystal layer. In the case where the stripe direction ofthe mask pattern is <1-100>, a nitride semiconductor film formedparticularly by an MOVPE method is laterally grown in a <11-20>direction vertical to the stripe direction, so that it is possible tobury the mask pattern with the nitride semiconductor thin film.Furthermore, depending upon growth characteristics, a threadingdislocation hardly appears on the mask pattern. It is understood fromthese characteristics that the <1-100> stripe direction is veryimportant for selective growth (lateral growth).

[0140] In the case where the stripe direction of the mask pattern isprescribed to be <11-20>, a nitride semiconductor crystal is laterallygrown in a direction of <1-100>. In this case, a lateral growth speed ofthe nitride semiconductor crystal is lower than that in the case wherethe stripe direction of the mask pattern is set to be <1-100>.Furthermore, a threading dislocation which comes from the openingportions of a mask is bent in the direction of the mask, and is combinedwith another threading dislocation to extend in the crystal growthdirection. Thus, compared with the case where the stripe direction ofthe mask pattern is prescribed to be <1-100>, a number of threadingdislocations are generated even in portions on the mask. However, thisdoes not mean that a new dislocation is generated immediately above themask, but that a threading dislocation which comes from the openingportions of the mask is dispersed. As a result, a threading dislocationdensity is reduced in the same way as in the case where the stripedirection is prescribed to be <1-100>. According to one embodiment, thestripe direction of the mask pattern is prescribed to be <1-100> or<11-20>, whereby a lateral growth is promoted and the mask pattern isburied efficiently; thus, a decrease in a threading dislocation densityand strain relaxation can be realized.

[0141] The n-th nitride semiconductor crystal layer may be made ofAl_(x)In_(y)Ga_(z)N (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z1). Such a crystal issuitable for the growth method of the present invention due to itsanisotropy (lateral growth).

[0142] It is preferable that the n-th nitride semiconductor crystallayer or the (n+1)-th nitride semiconductor crystal layer has athickness of about 5 μm or more. A threading dislocation generated fromthe substrate is blocked by a mask pattern, and enters a nitridesemiconductor film from the openings of the mask. However, by forming athick nitride semiconductor crystal layer, the mask pattern can becovered with a GaN film, and a threading dislocation which is notblocked can be reduced by the thick nitride semiconductor crystal layer.

[0143] Embodiment 8

[0144] In Embodiment 8, the GaN film 607 formed during the second stepin Embodiment 7 is evaluated for characteristics, in the case where theGaN film 607 is used as an underlying film of a device. Morespecifically, in Embodiment 7, mask formation and crystal growth on amask are repeated three times. Herein, the effect of the presentinvention will be described, in the case where mask formation andcrystal growth on a mask are repeated twice. In this case, the first andsecond mask patterns are formed so as to have an angle difference ofabout 120° from each other, so that lattice strains are reduced in twodirections vertical to the stripe directions of two mask patterns.However, a small number of lattice strains remain in a direction (i.e.,in a horizontal on the drawing surface of FIG. 8) which bisects an angleof about 120° formed by two mask patterns.

[0145] Furthermore, a threading dislocation density of the second GaNfilm 607 positioned immediately above the first and second mask patternsis reduced to about 10³/cm², and a threading dislocation density of theportions 609 in the second GaN film 607 grown from the opening portionsof the first mask pattern is about 10⁵/cm². An average threadingdislocation density on the entire surface of the second GaN film 607 isabout 3×10⁴/cm², which is a reduction of a threading dislocation byabout one order of magnitude, compared with the conventional example.Regarding strains, as described in Embodiment 7, more satisfactoryrelaxation effect is obtained compared with the conventional example(only the first step), by conducting the second step of the presentinvention.

[0146] Embodiment 9

[0147] Embodiment 9 is an altered example of Embodiment 8. Embodiment 9is the same as Embodiment 8, except that the stripe direction of thefirst mask pattern formed during the first step and the stripe directionof the second mask pattern formed during the second step have an angledifference of about 90°. FIG. 11A is a plan view of a GaN film formed inEmbodiment 9. For description, FIG. 11A shows mask patterns as seen fromthe top. As shown in FIG. 11A, the stripe direction of a first maskpattern 702 and the stripe direction of a second mask pattern 704 forman angle of about 90°. The first and second mask patterns 702 and 704are formed in a <11-20> direction and a <1-100> direction of a GaNcrystal, respectively. It is preferable that the first and second maskpatterns 702 and 704 are formed in a <11-20> direction and a <1-100>direction, respectively. However, the present invention is not limitedthereto.

[0148]FIG. 11B is a cross-sectional view taken along a line a-a′ in FIG.11A. First, a sapphire substrate 700 having a C-plane is placed in anMOVPE growth chamber, and a GaN layer 701 is grown to a thickness ofabout 2 μm, using TMG and NH₃ as materials. Then, in order to form afirst patterned mask, an SiO₂ film having a thickness of about 100 nm isformed by an EB vapor deposition method. Then, the SiO₂ film ispatterned to a periodic stripe (width: about 3 μm; pitch: about 7 μm) bya conventional photolithography method, whereby a first mask pattern 702is formed. As shown in FIG. 11A, The stripe direction of the first maskpattern 702 is prescribed to be <11-20> of a GaN crystal.

[0149] By using the substrate with the first mask pattern thus obtained,a first GaN film 703 is grown by a MOVPE method. More specifically, thefirst GaN film 703 is grown to a thickness of about 10 μm at a growthtemperature of about 1050° C., using TMG and NH₃ as materials, in apredetermined growth chamber. Thus, the first step is completed. Thefirst GaN film 703 starts growing from opening portions 706 of the firstmask pattern 702, and is laterally grown in a direction horizontal tothe substrate surface. Although a lateral growth speed is lower,compared with the case where the stripe direction of the mask pattern isprescribed to be <1-100> as in Embodiment 7 or 8, the GaN film 703having a thickness of about 10 μm is grown flat, covering the first maskpattern 702.

[0150] A threading dislocation density of the first GaN film 703 is onthe order of about 10⁶/cm² in the portions immediately above the firstmask pattern 702. However, a threading dislocation density of the firstGaN film 703 is on the order of about 10⁷/cm² in the portionsimmediately above the openings 706 of the first mask pattern 702.Compared with the case where the stripe direction of a mask pattern isprescribed to be <1-100>, a threading dislocation density in portionsimmediately above the mask pattern is larger by one to two orders ofmagnitude. Strains are relaxed in a direction vertical to the stripe ofthe mask pattern in the same way as in Embodiments 7 and 8.

[0151] Next, a second mask pattern 704 is formed on the first GaN film703. More specifically, an SiO₂ film having a thickness of about 100 nmis formed by an EB vapor deposition method in the same way as in thefirst mask pattern 702. The SiO₂ film is patterned to a periodic stripe(width: about 5 μm; pitch: about 7 μm) by a conventionalphotolithography method, whereby a second mask pattern 704 is formed. Asshown in FIG. 11A, the stripe direction of the second mask pattern 704is prescribed to be <1-100>. Furthermore, the stripe width of the secondmask pattern 704 is prescribed to be larger by about 2 μm than that ofthe first mask pattern 702.

[0152] Then, a second GaN film 705 is grown to a thickness of about 5 μmat a growth temperature of about 1050° C., using TMG and NH₃ asmaterials, in an MOVPE growth chamber. Thus, the second step iscompleted. The GaN film 705 is grown uniformly over the entire surfaceof the wafer.

[0153] A threading dislocation density of the entire second GaN film 705is on the order of 10⁵/cm², which is slightly lower than that of theconventional example. The direction of strains (including thermalstrains) caused in the first mask pattern 702 corresponds to thedirection in which strains are relaxed in the second mask pattern 704.Similarly, the direction of strains caused in the second mask pattern704 corresponds to the direction in which strains are relaxed in thefirst mask pattern 702. Thus, in Embodiment 9, there is a larger effectof removing strains, compared with Embodiments 7 and 8. Furthermore, asdescribed above in Embodiment 9, only the first and second steps areconducted. However, a third step may be conducted: a third mask patterncan be formed on the second GaN film 705 so as to cover the portionswhich cannot be covered with the first and second mask patterns, and athird GaN film can be formed. This can reduce a threading dislocationdensity from on the order of 10⁵/cm² to a threading dislocation densityon the order of 10⁴/cm².

[0154] In the present embodiment, the stripe directions of these maskpatterns are not equivalent. Therefore, equivalent selectivity and anequivalent relaxation function as in Embodiment 7 cannot be expected.However, since the stripe directions of the mask patterns form an angleof about 90°, there is a large effect of strain relaxation.

[0155] Embodiment 10

[0156] The purpose of Embodiment 10 is to form a thick GaN film on a GaNfilm having a mask pattern with a growth suppressing effect. In theprior art, a GaN substrate, which has an appropriate size andsatisfactory surface morphology intended for production of a nitridesemiconductor device, has not been provided. Embodiment 10 provides acrack-free GaN substrate

[0157]FIG. 12A is a cross-sectional view showing a structure of anitride semiconductor including a thick GaN film produced in Embodiment10. Reference numeral 800 denotes a nitride semiconductor (e.g., a GaNfilm) including a substrate produced by conducting n steps, using amethod for forming a GaN film described in Embodiments 7 to 9, and anuppermost surface 801 of the nitride semiconductor 800 denotes the n-thnitride semiconductor film (e.g., a GaN film) produced during the n-thstep. Reference numeral 802 denotes a thick GaN film produced by an HVPEmethod. The thick GaN film 802 may be produced by an MOVPE method,instead of the HVPE method. As shown in FIG. 12A, the nitridesemiconductor structure is composed of the nitride semiconductor 800including a substrate and the thick GaN film 802.

[0158] In Embodiment 10, the GaN film produced in Embodiment 7 will beexemplified as the nitride semiconductor 800 produced by n steps. Thenitride semiconductor 800 including a sapphire substrate produced inEmbodiment 7 is set in an HVPE apparatus. Then, in order to grow thethick GaN film 802, a V-group gas (which is a mixture of a NH₃ gas and acarrier H₂ gas) and a III-group gas (which is obtained by supplying anHCl gas onto Ga metal held in an HVPE apparatus at about 850° C. andmixing a III-group chloride (reaction product of Ga and an HCl gas witha carrier H₂ gas) are respectively supplied to an HVPE growth chamber inwhich the nitride semiconductor 800 is set. Thus, the thick GaN film 802is grown to a thickness of about 350 μm. The thick GaN film 802 is grownflat, and observation of the surface thereof with an optical microscopeshows that there are no cracks. Thus, a nitride semiconductor structureis formed.

[0159] A threading dislocation density of the thick GaN film 802produced in Embodiment 10 is on the order of 10³ to 10⁴/cm² which issubstantially the same or slightly lower than that of the GaN film whichis the nitride semiconductor 800 produced in Embodiment 7. The sameresults as those in Embodiment 7 are obtained with respect to strains.

[0160] In Embodiment 10, the uppermost surface 801 of the nitridesemiconductor (e.g., GaN film) 800 including a substrate produced duringthe n-th step is the n-th nitride semiconductor film (e.g., GaN film).However, as shown in FIG. 12B, the thick GaN film 802 may be formeddirectly on the n-th mask pattern 803. For example, in the case of usingthe nitride semiconductor 800 produced as in Embodiment 7, the thick GaNfilm is directly on the third mask pattern, and in the case of using thenitride semiconductor 800 produced as in Embodiment 8 or 9, the thickGaN film is directly on the second mask pattern. Characteristics ofthese crystals are the same as those in Embodiment 10.

[0161] A semiconductor structure including a sapphire substrate producedin Embodiment 10 can also be used as a substrate. Also, the sapphiresubstrate may be peeled off from the semiconductor structure by grindingor etching, or by utilizing thermal strains, and the remaining structurecan be used as a GaN substrate. When such a GaN substrate is used, thethick GaN film 802 may be used as a substrate. Furthermore, a GaNsubstrate, which is obtained by removing the sapphire substrate andgrinding or etching a part of the nitride semiconductor structure, maybe used. For example, the n-th nitride semiconductor film which is theuppermost surface can be used as a substrate.

[0162] In the prior art, it is difficult to provide a nitridesemiconductor substrate having an appropriate size and satisfactorysurface morphology intended for device production. However, by removingat least the sapphire substrate from a crystal structure including anitride semiconductor crystal layer, it becomes possible to provide anitride semiconductor substrate which satisfies the requirements ofdevice production by a simple procedure.

[0163] Furthermore, the crystal growth method including theabove-mentioned steps has an effect of relaxing strains, in addition todecreasing a threading dislocation density. The strains are caused by adifference in a coefficient of thermal expansion as well as a differencein a lattice constant between the substrate and the nitridesemiconductor crystal. For example, it is known that in the case where athick nitride semiconductor is grown directly on a sapphire substrate,cracks (about 20 μm) are formed during a temperature decrease step atthe end of crystal growth due to a difference in a coefficient ofthermal expansion. However, by using the above-mentioned crystal growthmethod of the present invention, a thick nitride semiconductor film canbe formed on a sapphire substrate without forming cracks.

[0164] Embodiment 11

[0165]FIG. 13 shows a structure of a semiconductor laser device producedin Embodiment 11. The elements denoted by reference numerals 600 to 612shown in FIG. 13 are the same as those in Embodiment 7.

[0166] The semiconductor laser device in the present embodiment includesan n-GaN contact layer 650, an Al_(0.1)Ga_(0.9)N cladding layer 614, ann-GaN optical guide layer 615, a multi quantum-well structure activelayer 616 including 5 In_(0.2)Ga_(0.8)N quantum-well layers and 6In_(0.05)Ga_(0.95)N barrier layers, an Al_(0.2)Ga_(0.8)N evaporationpreventing layer 617, a p-GaN optical guide layer 618, ap-Al_(0.1)Ga_(0.9)N cladding layer 619, a p-GaN contact layer 620, ap-type electrode 621, an n-type electrode 622, and an SiO₂ insulatingfilm 623.

[0167] According to the present invention, the surface of the sapphiresubstrate 600 may have another orientation, such as an a-plane, anr-plane, and an m-plane. Furthermore, a GaN substrate, an SiC substrate,a spinnel substrate, an MgO substrate, an Si substrate, and a GaAssubstrate can be used in place of a sapphire substrate. Particularly inthe case of using a GaN substrate, compared with the case of using asapphire substrate, at least the following advantages are obtained: adifference in a lattice constant between the substrate and a galliumnitride type semiconductor material deposited on the substrate issmaller, and a film with satisfactory crystallinity can be obtained.Furthermore, the GaN substrate is more likely to be cleaved, so that itis easier to produce a laser resonator by cleavage. The cladding layers614 and 619 maybe made of a mixed crystal containing three elements(AlGaN) having an Al mole fraction other than Al_(0.1)Ga_(0.9)N. In thiscase, when an Al mole fraction is increased, a difference in an energygap and a difference in a refractive index between the active layer andthe cladding layer becomes larger, so that carriers and light areconfined in the active layer, which further decreases an oscillationthreshold current and improves temperature characteristics. Furthermore,when an Al mole fraction is decreased to such a degree that carriers andlight can be confined, the mobility of carriers in the cladding layerbecomes large. Therefore, the resistance of a semiconductor laser devicecan be decreased. Furthermore, the cladding layers 614 and 619 may bemade of a mixed crystal semiconductor containing a trace amount ofanother element in addition to the above-mentioned three elements, andthe mole fractions of a mixed crystal are not required to be the samebetween the cladding layer 614 and the cladding layer 619.

[0168] The optical guide layers 615 and 618 may be made of any materialwhich allows an energy gap therebetween to have a value between anenergy gap of the quantum-well layers included in the active layer 616and a energy gap of the cladding layers 614 and 619. For example, amixed crystal containing three elements (e.g., InGaN or AlGaN) may beused. Furthermore, it is not necessary to dope a donor or an acceptorover the entire optical guide layers 615 and 618, and only a portionthereof on the side of the active layer 616 may be non-doped.Furthermore, the entire guide layers 615 and 618 may be non-doped. Inthis case, there is an advantage in that the number of carriers presentin the optical guide layers 615 and 618 becomes small, light absorptionby free carriers is decreased, and an oscillation threshold current canbe further reduced.

[0169] With the quantum-well layers and the barrier layers included inthe active layer 616, mole fractions should be set in accordance with arequired laser oscillation wavelength. In the case where it is desirableto make an oscillation wavelength longer, the In mole fraction of thequantum-well layers is increased. In the case where it is desired toshorten an oscillation wavelength, the In mole fraction of thequantum-well layers is decreased. Furthermore, the quantum-well layersand the barrier layers may be made of a mixed crystal semiconductorcontaining four or more elements including a trace amount of anotherelement in addition to a mixed crystal containing three elements(InGaN). The barrier layers may be made of GaN.

[0170] In the present embodiment, the evaporation preventing layer 617is formed in contact with the active layer 616. The purpose of this isto prevent In contained in the active layer 616 from evaporating duringan increase in growth temperature. Therefore, any material can be usedfor the evaporation preventing layer 617 as long as it protects theactive layer 616. For example, a mixed crystal containing three elements(AlGaN) having another Al mole fraction and GaN may be used.Furthermore, Mg may be doped into the evaporation preventing layer 617.In this case, there is an advantage that holes can be easily injectedfrom the optical guide layer 618 and the cladding layer 619.Furthermore, in the case where the In mole fraction of the quantum-welllayers included in the active layer 616 is small, a change in the Inmole fraction in the active layer 616 due to evaporation of In is small,so that the evaporation preventing layer 617 is not required to beformed. Even if the evaporation preventing layer 617 is not formed,characteristics of a gallium nitride type semiconductor laser device inthe present embodiment will not be impaired.

[0171] Hereinafter, a method for producing the above-mentioned galliumnitride type semiconductor laser device will be described with referenceto FIG. 13.

[0172] In the following description, the case of using a MOVPE method isshown. However, any method which is capable of epitaxially growing GaNmay be used. For example, another crystal growth method such as MBE orHVPE can be used.

[0173] First, the contact layer 650 doped with Si is grown to athickness of about 3 μm at a growth temperature of about 1050° C., usingTMG, NH₃, and SiH₄ as materials, on the substrate produced in Embodiment7 placed in a predetermined growth chamber. Then, TMA is added to thematerials, and the cladding layer 614 doped with Si is grown to athickness of about 0.4 μm at a growth temperature of about 1050° C. TMAis removed from the materials, and the optical guide layer 615 dopedwith Si is grown to a thickness of about 0.1 μm at a growth temperatureof about 1050° C.

[0174] Next, the growth temperature is lowered to about 750° C., and 5barrier layers (thickness: about 3 nm) and 5 quantum-well layers(thickness: about 2 nm) are alternately grown and the barrier layer(thickness: about 3 nm) is grown, using TMG, NH₃ and TMI, whereby theactive layer 616 (total thickness: about 28 nm) is produced. Then, theevaporation preventing layer 617 is grown to a thickness of about 30 nmat a growth temperature of about 750° C., using TMG, TMA, and NH₃ asmaterials.

[0175] Next, the growth temperature is raised to about 1050° C., and theoptical guide layer 618 doped with Mg is grown to a thickness of about0.1 μm, using TMG, NH₃, and bisethylcyclopentadienyl magnesium (EtCP₂Mg)as materials. TMA is added to the materials, and the cladding layer 619doped with Mg is grown to a thickness of about 0.4 μm at a growthtemperature of about 1050° C. TMA is removed from the materials, and thecontact layer 620 doped with Mg is grown to a thickness of about 0.5 μmat a growth temperature of about 1050° C. Thus, an epitaxial waferhaving a gallium nitride type laser device structure is completed.Thereafter, the wafer is annealed in a nitrogen gas atmosphere at about800° C., whereby the Mg-doped p-type layers are rendered low-resistant.

[0176] Furthermore, etching is conducted from the top surface of thecontact layer 620 so as to obtain a stripe shape (width: about 200 μm)by using conventional photolithography and dry etching until the contactlayer 650 is exposed, whereby a mesa structure is produced. Next, usingthe photolithography and dry etching similar to the above, the remainingcontact layer 620 and the cladding layer 619 are etched. At this time, astripe-shaped ridge structure should be positioned about 3 μm or moreaway from both ends of the mesa structure with a width of about 200 μm.In the present embodiment, the ridge structure is formed about 10 μmaway from the end of the mesa structure on the side where the n-typeelectrode 622 is to be formed. If the ridge structure is positioned soas to be close to the n-type electrode 622 as described above, theelectric resistance of a device is decreased, and the working voltage isreduced. Furthermore, the dry etching is stopped so as not to etch theactive layer 616. Thus, the active layer 616 is protected from etchingdamage, which prevents a decrease in reliability and an increase in anoscillation threshold current.

[0177] The insulating film 623 is formed to a thickness of about 200 nmas a current blocking layer on the side surfaces of the ridge structureand on the surface of the p-type layer excluding the ridge. The p-typeelectrode 621 made of nickel and gold is formed on the surface of theinsulating layer 623 and the contact layer 620, and the n-type electrode622 made of titanium and aluminum is formed on the surface of thecontact layer 650 exposed by etching. Thus, a gallium nitride type laserdevice wafer is completed.

[0178] Thereafter, the wafer thus obtained is cleaved in a directionvertical to the ridge stripe to form a resonance plane, and the wafer isdivided into chips. Each chip is mounted on a stem, and each electrodeis connected to each lead terminal by wire bonding. Thus, a galliumnitride type semiconductor laser device is completed.

[0179] In the semiconductor laser device produced as described above,satisfactory laser characteristics (oscillation wavelength: about 410nm; oscillation threshold value: about 50 mA) are obtained. Furthermore,due to a decrease in crystal defects, the semiconductor laser devicethus obtained is highly reliable (about 900 hours at about 60° C.).Furthermore, a ratio of laser devices having crystal defects isremarkably decreased, with a yield being about 80% or higher.

[0180] In the present embodiment, thicknesses of each quantum-well layerand each barrier layer included in the active layer 616 are about 2 nmand about 3 nm, respectively. However, as long as the thickness of eachquantum-well layer and each barrier layer is prescribed to be about 10nm or less, the same effects can be obtained irrespective ofembodiments. Furthermore, the number of quantum-well layers in theactive layer 616 may be 3 or 4. Alternatively, a single quantum-wellstructure active layer may be used.

[0181] In the present embodiment, sapphire, which is an insulator, isused for the substrate, so that the n-type electrode 622 is formed onthe surface of the contact layer 650 exposed by etching. However, ifGaN, SiC, Si, GaAs, or the like having an n-type conductivity is used,the n-type electrode 622 may be formed on the reverse surface of thesubstrate. In this case, the mesa structure with a width of about 200 μmshould be positioned at least about 3 μm away from both ends of thesemiconductor laser device chip. P-type structures and n-type structuresmay be reversed.

[0182] Furthermore, GaN used in the crystal growth method of the presentinvention can also be applied to a power device dealing with a largecurrent (i.e., a device in the field of hard electronics such as a GaNFET device and an AlGaN/GaN HEMT device). In the case where a nitridesemiconductor is applied to a power device, thermal strains caused byheat generation due to a large current are combined with strains presentin the device, which has an adverse effect to reliability of the device.Therefore, in particular, the crystal growth method of the presentinvention is advantageous.

[0183] As described above, in a semiconductor substrate including agallium nitride crystal layer produced according to the presentinvention, a film made of a growth suppressing material and a nitridesemiconductor film are formed on different surfaces, using a reversemask pattern, so that growth of a threading dislocation is prevented.Thus, a crystal having very small crystal defect density (about 10⁴/cm²or less) is obtained. A gallium nitride semiconductor laser device usingsuch a crystal can be produced with highly reliability and good yield ata low production cost.

[0184] Alternatively, in a semiconductor substrate including a galliumnitride crystal layer produced according to the present invention, filmsmade of a growth suppressing material and nitride semiconductor filmsare alternately formed. Thus, a crystal with little strains and a verysmall threading dislocation density (about 10⁴/cm² or less) is obtained.A gallium nitride semiconductor laser using such a crystal can also beproduced with high reliability and good yield.

[0185] Various other modifications will be apparent to and can bereadily made by those skilled in the art without departing from thescope and spirit of this invention. Accordingly, it is not intended thatthe scope of the claims appended hereto be limited to the description asset forth herein, but rather that the claims be broadly construed.

What is claimed is:
 1. A method for producing a semiconductor substrate,comprising the steps: forming a first patterned mask containing amaterial having a growth suppressing effect on a lower substrate;growing a semiconductor crystal on the lower substrate via the firstpatterned mask to form a first semiconductor crystal layer; forming asecond patterned mask containing a material having a growth suppressingeffect on or above the lower substrate, the second patterned mask atleast having a surface which is positioned at a level different from alevel of a surface of the first patterned mask, with respect to asurface of the lower substrate; and growing a semiconductor crystal onor above the lower substrate via the second patterned mask to form asecond semiconductor crystal layer.
 2. A method for producing asemiconductor substrate according to claim 1 , wherein the secondpatterned mask is positioned on the first semiconductor crystal layer.3. A method for producing a semiconductor substrate according to claim 1, wherein the first and second patterned masks are patterned in such amanner that a combination of the first and second patterned masks coversthe entire surface of the lower substrate, and an area of the lowersubstrate covered with the second patterned mask is larger than an areaof the lower substrate covered with the first patterned mask.
 4. Amethod for producing a semiconductor substrate according to claim 1 ,wherein the second patterned mask includes a first portion and a secondportion, the first and second portions have different widths in adirection vertical to the surface of the lower substrate, and the stepof forming the first semiconductor crystal layer and the step of formingthe second semiconductor crystal layer are conducted during the samecrystal growth step.
 5. A method for producing a semiconductor substrateaccording to claim 4 , wherein the first portion of the second patternedmask is at least partially positioned on the first patterned mask, andthe second patterned mask has an L-shape.
 6. A method for producing asemiconductor substrate according to claim 5 , wherein the first portionof the second patterned mask is at least partially positioned on thelower substrate, and the second patterned mask has a T-shape.
 7. Amethod for producing a semiconductor substrate according to claim 1 ,wherein a growth direction of the second semiconductor crystal layer isat least partially different from a growth direction of the firstsemiconductor crystal layer.
 8. A method for producing a semiconductorsubstrate according to claim 1 , wherein the first semiconductor crystallayer is formed in the vicinity of openings in the first patterned mask,whereby the first semiconductor crystal layer has openings on the lowersubstrate and the first patterned mask.
 9. A method for producing asemiconductor substrate according to claim 1 , wherein the lowersubstrate includes a sapphire substrate and a lower semiconductorcrystal layer provided on an upper side of the sapphire substrate in acrystal growth direction.
 10. A method for producing a semiconductorsubstrate according to claim 1 , wherein the material having a growthsuppressing effect is selected from the group consisting of SiO₂ andSiN_(x), and the first and second patterned masks are independentlyselected from the group consisting of SiO₂ and SiN_(x).
 11. A method forproducing a semiconductor substrate according to claim 1 , wherein thefirst and second semiconductor crystal layers are selected from thegroup consisting of GaN, InGaN, and AgGaN.
 12. A semiconductorsubstrate, comprising: a first patterned mask containing a materialhaving a growth suppressing effect, provided on a lower substrate; afirst semiconductor crystal layer grown on the lower substrate via thefirst patterned mask; a second patterned mask containing a materialhaving a growth suppressing effect, provided on or above the lowersubstrate, at least having a surface which is positioned at a leveldifferent from a level of a surface of the first patterned mask, withrespect to a surface of the lower substrate; and a second semiconductorcrystal layer grown on or above the lower substrate via the secondpatterned mask.
 13. A method for producing a semiconductor substrate,comprising the steps of: forming an n-th patterned mask containing amaterial having a growth suppressing effect on or above a lowersubstrate, wherein n is an integer of 1 or more; growing a nitridesemiconductor crystal on or above the lower substrate via the n-thpatterned mask to form an n-th nitride semiconductor crystal layer;forming an (n+1)-th patterned mask containing a material having a growthsuppressing effect on or above the lower substrate, the (n+1)-thpatterned mask at least having a surface which is positioned at a leveldifferent from a level of a surface of the n-th patterned mask, withrespect to a surface of the lower substrate; and growing a nitridesemiconductor crystal on or above the lower substrate via the (n+1)-thpatterned mask to form an (n+1)-th nitride semiconductor crystal layer.14. A method for producing a semiconductor substrate according to claim13 , wherein the first to (n+1)-th patterned masks are patterned in sucha manner that a combination of the first to (n+1)-th patterned maskscovers the entire surface of the lower substrate.
 15. A method forproducing a semiconductor substrate according to claim 13 , wherein then-th patterned mask and the (n+1)-th patterned mask are respectivelypatterned in a stripe shape, and a direction of the stripe of the n-thpatterned mask is twisted from a direction of the stripe of the (n+1)-thpatterned mask.
 16. A method for producing a semiconductor substrateaccording to claim 15 , wherein the direction of the stripe of the n-thpatterned mask and the direction of the stripe of the (n+1)-th patternedmask have an angle difference of about 120°.
 17. A method for producinga semiconductor substrate according to claim 15 , wherein the directionof the stripe of the n-th patterned mask and the direction of the stripeof the (n+1)-th patterned mask have an angle difference of about 90°.18. A method for producing a semiconductor substrate according to claim15 , wherein a width of the stripe of the (n+1)-th patterned mask isequal to or larger than a width of the stripe of the n-th patternedmask.
 19. A method for producing a semiconductor substrate according toclaim 13 , wherein the material having a growth suppressing effect ismade of SiO₂ or SiN_(x), and the first to (n+1)-th patterned masks areindependently made of SiO2 or SiN_(x).
 20. A method for producing asemiconductor substrate according to claim 15 , wherein the lowersubstrate includes at least a lower nitride semiconductor crystal layerprovided on an upper surface of the lower substrate, and a direction ofthe stripe of the n-th patterned mask is equal to a <1-100> direction ora <11-20> direction of a crystal of the nitride semiconductor crystallayer.
 21. A method for producing a semiconductor substrate according toclaim 15 , wherein the lower substrate includes at least a lower nitridesemiconductor crystal layer provided on an upper side of the lowersubstrate in a crystal growth direction, the semiconductor substrateincludes the first, second and third nitride semiconductor crystallayers, and a combination of directions of the first, second and thirdpatterned masks consists of a combination of [1-100], [10-10], and[01-10] directions of a crystal of the nitride semiconductor crystal.22. A method for producing a semiconductor substrate according to claim13 , wherein the n-th nitride semiconductor crystal layer is made ofAl_(x)In_(y)Ga_(z)N (where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1).
 23. Amethod for producing a semiconductor substrate according to claim 13 ,wherein the n-th nitride semiconductor crystal layer or the (n+1)-thnitride semiconductor crystal layer has a thickness of about 5 μm ormore.
 24. A method for producing a semiconductor substrate according toclaim 13 , wherein the lower substrate includes a substrate body and alower nitride semiconductor crystal layer provided on an upper side ofthe substrate body in a crystal growth direction, the method furthercomprising the step of removing at least the substrate body from acrystal structure including the (n+1)-th nitride semiconductor crystallayer after the step of forming the (n+1)-th nitride semiconductorcrystal layer.
 25. A semiconductor substrate, comprising: an n-thpatterned mask containing a material having a growth suppressing effectprovided on or above a lower substrate, wherein n is an integer of 1 ormore; an n-th nitride semiconductor crystal layer grown on or above thelower substrate via the n-th mask; an (n+1)-th patterned mask containinga material having a growth suppressing material provided on or above thelower substrate, the (n+1)-th mask at least having a surface which ispositioned at a level different from a level of a surface of the n-thmask, with respect to a surface of the lower substrate; and an (n+1)-thnitride semiconductor crystal layer grown on or above the lowersubstrate via the (n+1)-th patterned mask.
 26. A light-emitting deviceproduced by using the semiconductor substrate of claim 25 .